In the more general case, "nab" typically has a negative connotation but it isn't always related to the person who was nabbed. More specifically, "nab" simply implies that the person who was nabbed didn't want to be caught or interrupted.
In the specific context you give, is a good example of when the negative connotation is applied to the person who did the nabbing:
I was the guy who nabbed you as you were leaving to ask about ...
"Nabbed" in this context is most similar to "interrupted". Since you are the one who did the nabbing it would read a little tongue-in-cheek and probably wouldn't be interpreted very negatively. If anything, referring to the interruption as "nabbing" would acknowledge that their time is valuable and they may not want to be interrupted.
One more note on "nab" is that you can "nab" objects and this usage nearly always carries a negative connotation. The definition you quote uses such an example:
Dan nabbed the seat next to mine.